Environmental Science and Pollution Research

, Volume 25, Issue 17, pp 16913–16921 | Cite as

Reduction mechanism of hexavalent chromium by functional groups of undissolved humic acid and humin fractions of typical black soil from Northeast China

  • Jia Zhang
  • Huilin Yin
  • Hui Wang
  • Lin Xu
  • Barnie Samuel
  • Fei Liu
  • Honghan Chen
Research Article


Soil organic matters (SOM) have a great retention effect on Cr(VI) migration in subsurface environment, which act as the main electron donors for Cr(VI) reduction; however, Cr(VI) reduction mechanism by different SOM fractions is still unclear, such as undissolved humic acid (HA) and humin (HM). In this study, HA and HM fractions extracted from typical black soil from Northeast China were used to investigate the reaction mechanism between humus functional groups and Cr(VI). According to the results, phenol and hydroxyl were determined as the main electron donors for Cr(VI) reduction by HA and HM instead of carboxyl and carbonyl, which were more likely involved in Cr complexation. Furthermore, Cr(VI) reduction was more dependent on aromatic carbon, rather than aliphatic carbon, and functional groups on the particle surfaces of HA and HM were much more active for Cr(VI) reduction than their interior part. Additionally, HM was found to have a relatively low Cr(VI) reduction capability compared with HA resulting from its high content of cellulose structures that are quite resistant to Cr(VI) oxidation. These results suggest that in the soil environment, undissolved HA tends to play a much more important role than HM in Cr(VI) reduction and retention in the condition that their mass contents are comparable.


Humic acid Humin Functional groups Hexavalent chromium Reduction 



This work was financially supported by the National Natural Science Foundation of China (Grant 41672239) and China Geological Survey (1212011121173).


  1. Al-Abadleh HA, Mifflin AL, Bertin PA, Nguyen ST, Geiger FM (2005) Control of carboxylic acid and ester groups on chromium (VI) binding to functionalized silica/water interfaces studied by second harmonic generation. J Phys Chem B 109:9691–9702. CrossRefGoogle Scholar
  2. Bonin JL, Simpson MJ (2007) Variation in phenanthrene sorption coefficients with soil organic matter fractionation: the result of structure or conformation? Environ Sci Technol 41:153–159. CrossRefGoogle Scholar
  3. Brose DA, James BR (2010) Oxidation-reduction transformations of chromium in aerobic soils and the role of electron-shuttling quinones. Environ Sci Technol 44:9438–9444. CrossRefGoogle Scholar
  4. Dermentzis K, Christoforidis A, Valsamidou E, Lazaridou A, Kokkinos N (2011) Removal of hexavalent chromium from electroplating wastewater by electrocoagulation with iron electrodes. Global Nest J 13:412–418Google Scholar
  5. Dhal B, Thatoi HN, Das NN, Pandey BD (2013) Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: a review. J Hazard Mater 250-251C:272–291. CrossRefGoogle Scholar
  6. Fanning PE, Vannice MA (1993) A drifts study of the formation of surface groups on carbon by oxidation. Carbon 31:721–730. CrossRefGoogle Scholar
  7. Fendorf SE (1995) Surface reactions of chromium in soils and waters. Geoderma 67:55–71. CrossRefGoogle Scholar
  8. Hsu CL, Wang SL, Tzou YM (2007) Photocatalytic reduction of Cr(VI) in the presence of NO3- and cl- electrolytes as influenced by Fe(III). Environ Sci Technol 41:7907–7914. CrossRefGoogle Scholar
  9. Hsu NH, Wang SL, Lin YC, Sheng GD, Lee JF (2009) Reduction of Cr(VI) by crop-residue-derived black carbon. Environ Sci Technol 43:8801–8806. CrossRefGoogle Scholar
  10. Hsu LC, Wang SL, Lin YC, Wang MK, Chiang PN, Liu JC, Kuan WH, Chen CC, Tzou YM (2010) Cr(VI) removal on fungal biomass of Neurospora crassa: the importance of dissolved organic carbons derived from the biomass to Cr(VI) reduction. Environ Sci Technol 44:6202–6208. CrossRefGoogle Scholar
  11. Hu W, Mao J, Baoshan Xing A, Schmidtrohr K (2016) Poly(methylene) Crystallites in Humic Substances Detected by Nuclear Magnetic Resonance. Environ Sci Technol 34:530–534. CrossRefGoogle Scholar
  12. Janos P, Hula V, Bradnova P, Pilarova V, Sedlbauer J (2009) Reduction and immobilization of hexavalent chromium with coal- and humate-based sorbents. Chemosphere 75:732–738. CrossRefGoogle Scholar
  13. Jardine PM, Fendorf SE, Mayes MA, Larsen IL, Brooks SC, Bailey WB (1999) Fate and transport of hexavalent chromium in undisturbed heterogeneous soil. Environ Sci Technol 33:2939–2944. CrossRefGoogle Scholar
  14. Kang S, Amarasiriwardena D, Veneman P, Xing (2003) Characterization of ten sequentially extracted humic acids and a humin from a soil in western Massachusetts. Soil Sci 168:880–887. CrossRefGoogle Scholar
  15. Kimbrough DE, Cohen Y, Winer AM, Creelman L, Mabuni C (1999) A critical assessment of chromium in the environment. C R C. Crit Rev Environ Control 29:1–46. CrossRefGoogle Scholar
  16. Kožuh N, Štupar J, Gorenc B (2000) Reduction and oxidation processes of chromium in soils. Environ Sci Technol 34:112–119. CrossRefGoogle Scholar
  17. Li L, Huang W, Peng PA, Sheng G, Fu J (2003) Chemical and molecular heterogeneity of humic acids repetitively extracted from a peat. Soil Sci Soc Am J 67:740–746. CrossRefGoogle Scholar
  18. Li Y, Yue Q, Gao B, Li Q, Li C (2008) Adsorption thermodynamic and kinetic studies of dissolved chromium onto humic acids. Colloids Surfaces B Biointerfaces 65:25–29. CrossRefGoogle Scholar
  19. Liu J, Zhang XH, Tran H, Wang DQ, Zhu YN (2011) Heavy metal contamination and risk assessment in water, paddy soil, and rice around an electroplating plant. Environ Sci Pollut Res 18:1623–1632. CrossRefGoogle Scholar
  20. Nickens KP, Patierno SR, Ceryak S (2010) Chromium genotoxicity: a double-edged sword. Chem Biol Interact 188:276–288. CrossRefGoogle Scholar
  21. O'Reilly JM, Mosher RA (1983) Functional groups in carbon black by FTIR spectroscopy. Carbon 21:47–51. CrossRefGoogle Scholar
  22. Raddatz AL, Johnson TM, Mcling TL (2011) Cr stable isotopes in Snake River plain aquifer groundwater: evidence for natural reduction of dissolved Cr(VI). Environ Sci Technol 45:502–507. CrossRefGoogle Scholar
  23. Sellitti C, Koenig JL, Ishida H (1990) Surface characterization of graphitized carbon-fibers by attenuated total reflection fourier-transform infrared-spectroscopy. Carbon 28:221–228. CrossRefGoogle Scholar
  24. Simpson AJ, Song G, Smith E, Lam B, Novotny EH, Hayes MH (2007) Unraveling the structural components of soil humin by use of solution-state nuclear magnetic resonance spectroscopy. Environ Sci Technol 41:876–883. CrossRefGoogle Scholar
  25. Tang J, Petersen E, Weber WJ (2008) Development of engineered natural organic sorbents for environmental applications. 4. Effects on biodegradation and distribution of pyrene in soils. Environ Sci Technol 42: 1283–1289.
  26. Van ZA, Comans RN (2007) Measurement of humic and fulvic acid concentrations and dissolution properties by a rapid batch procedure. Environ Sci Technol 41:6755–6761. CrossRefGoogle Scholar
  27. Vanderhart DL, Atalla RH (1984) Studies of microstructure in native celluloses using solid-state carbon-13 NMR. Macromolecules 17:1465–1472. CrossRefGoogle Scholar
  28. Wang T, Hong M (2015) Solid-state NMR investigations of cellulose structure and interactions with matrix polysaccharides in plant primary cell walls. J Exp Bot 20:333–338. Google Scholar
  29. Wang X, Guo X, Yang Y, Tao S, Xing B (2011) Sorption mechanisms of phenanthrene, lindane, and atrazine with various humic acid fractions from a single soil sample. Environ Sci Technol 45:2124–2130. CrossRefGoogle Scholar
  30. Watanabe A, Kuwatsuka S (1991) Triangular diagram for humus composition in various types of soils. Soil Sci Plant Nutrition 37:167–170. CrossRefGoogle Scholar
  31. Wittbrodt PR, Palmer CD (1996) Effect of temperature, ionic strength, background electrolytes, and Fe(III) on the reduction of hexavalent chromium by soil humic substances. Environ Sci Technol 30:2470–2477. CrossRefGoogle Scholar
  32. Xiao W, Zhang Y, Li T, Chen B, Wang H, He Z, Yang X (2012) Reduction kinetics of hexavalent chromium in soils and its correlation with soil properties. J Environ Qual 41:1452–1458. CrossRefGoogle Scholar
  33. Xing B (2001) Sorption of naphthalene and phenanthrene by soil humic acids. Environ Pollut 111:303–309. CrossRefGoogle Scholar
  34. Yang Y, Shu L, Wang X, Xing B, Tao S (2011) Impact of de-ashing humic acid and humin on organic matter structural properties and sorption mechanisms of phenanthrene. Environ Sci Technol 45:3996–4002. CrossRefGoogle Scholar
  35. Zhang JH, He MC, Shi YH (2009a) Comparative sorption of benzo[α]phrene to different humic acids and humin in sediments. J Hazard Mater 166:802–809. CrossRefGoogle Scholar
  36. Zhang JJ, Dou S, Song XY (2009b) Effect of long-term combined nitrogen and phosphorus fertilizer application on 13C CPMAS NMR spectra of humin in a Typic hapludoll of Northeast China. Eur J Soil Sci 60:966–973. CrossRefGoogle Scholar
  37. Zhang J, Wang S, Wang Q, Wang N, Li C, Wang L (2013) First determination of cu adsorption on soil humin. Environ Chem Lett 11:41–46. CrossRefGoogle Scholar
  38. Zhang J, Chen L, Yin H, Jin S, Liu F, Chen H (2017a) Mechanism study of humic acid functional groups for Cr(VI) retention: two-dimensional FTIR and (13)C CP/MAS NMR correlation spectroscopic analysis. Environ Pollut 225:86–92. CrossRefGoogle Scholar
  39. Zhang J, Yin H, Chen L, Liu F, Chen H (2017b) The role of different functional groups in a novel adsorption-complexation-reduction multi-step kinetic model for hexavalent chromium retention by undissolved humic acid. Environ Pollut.
  40. Zhang J, Yin H, Samuel B, Liu F, Chen H (2018) A novel method of three-dimensional hetero-spectral correlation analysis for the fingerprint identification of humic acid functional groups for hexavalent chromium retention. RSC Adv 8:3522–3529. CrossRefGoogle Scholar
  41. Zhao TT, Ge WZ, Nie YX, Wang YX, Zeng FG, Qiao Y (2016) Highly efficient detoxification of Cr(VI) by brown coal and kerogen: process and structure studies. Fuel Process Technol 150:71–77. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Jia Zhang
    • 1
  • Huilin Yin
    • 1
  • Hui Wang
    • 1
  • Lin Xu
    • 1
  • Barnie Samuel
    • 1
  • Fei Liu
    • 1
  • Honghan Chen
    • 1
  1. 1.Beijing Key Laboratory of Water Resources and Environmental EngineeringChina University of GeosciencesBeijingPeople’s Republic of China

Personalised recommendations